Esters of glycol monoesters and acylated hydroxy acids



UNITED STATES PATENT OFFICE harass or GLYCOL MoNoss'rEas lum ACYLATED maoxr ACIDS Thomas F. Carruthers, South Charleston, and Charles M. Blair, Charleston, W. Va., cul -nor:

to Carbide and Carbon Chemical: Corporation, a corporation of New York No Drawing. Application January 16, 1936. Serial No. 59,406

14 Claims. (01. 280-484) The invention relates to new chemical comaction temperature was 159 C. To 1866 grams pounds comprising esterification products of a of this first reaction product there was then glycol monoester and an acylated hydroxy acid. added 856 grams of acetic anhydride, and the It has particular reference to ester compositions mixture was heated to 135 C. for two hours.

formed by the reaction of a carboxylic acid mono- After rem vi x s ac i n y i nd acid ester of an alkylene or polyalkylene glycol, a hyby vacuum distillation, the crude product was droxy monobasic or polybasic acid, and an alineutralized by washing with aqueous sodium carphatic monocarboxylic acid, or its anhydride. bonate solution. It was then washed twice with These new esters are stable liquid compositions water, and dried by heating under reduced preshaving properties of value as solvents and plassure. The final. completely esterifled P duct ticizing agents in lacquers and plastic ccmposiwas a straw colored, very viscous liquid, insoluble tions employing cellulose derivatives, or natural in water. The saponification equivalent was 84.5,

and synthetic gums and resins. and the molecular weight 470, as determined by v From their method of. preparation, the nature elevation of boiling point. This ester may be and structure of the compounds will be quite called dl-(diethylene glycol monoacetate) diacetyl 15 evident. This consists preferably in a reaction oi tartrate. two steps, in which a glycol mcnoester is first Example II reacted with a hydroxy monobasic or polybasic By a procedure substantially similar to the acid,- to efiect esterification of each carboxyl above example, 383 grams (25 mols) of propylene group 01 the acid- The hydroxyl groups of t glycol monobutyrate were heated with 2'78 grams 0 acid radical are then acylated by iurther reaction (26 mols) of 85% lactic acid in the presence of with a suitable acyl group, to produce a stable anhydrous aluminum sulfate as a catalyst The mixed ester compound. The hydroxy acids suitmaximum reaction temperature is C The able in this reaction will include those containing entire product was then further heated to i 0 9 hydmxyl gmups' and which are m- 1.5 hours with 420 grams (2.7 mols) of butyric 25 monobasic or polybasic in nature. Representaanhydflde The final product obtained by tive of these are lactic, glycolic, malic, citric, nation under reduced pressdre was a water tartaric among the aliphatic acids, as well as saliwhite liquid of a faint pleasant odor It had a cylic, hydroxynaphthoic and similar aromatic despecific gravity of 1.054 at t s Q sapomm 30 rivatives. Aliphatic monocarboxylic acid monocation equivalent of 97 3 and a boning point of 30 esters of both the alkylene and polyalkylene gly- C. at 3 mm. u' This ester compound cols will function as described. Many of these may be named propylene glycol monobutymte are known, such as the monoacetate and monobutml lactate butyrate ester of ethylene glycol, propylene glycol, diethylene glycol, and the like. For the Example III 35 acylation of the hydroxy acid ester, acetic acid, Ethylene glycol monoacetate lactate was butyric acid, or other lower aliphatic monobasic pared in a manner similar to that described acids as weuras their anhydfldes may be usedabove. To 185 grams of this ester were slowly Aromatic monobasic acids, such as benzoic or added 140 grams 0! bemoyl chloride at a 40 naphthoic acids, are suitable, and certain acylatperature of Q This reaction mixture was 40 8 agents other than carboxync compounds may then heated for an hour at 100 to 110 C., and be usedexample, acid halides including thereafter neutralized by agitating it with an acetyl chloride and benzoyl chloride, or metallic aqueous Solution of sodium carbonate. salts 01 1110110135810 acids may be employed in Distillation o! the neutralized reaction mixture methods customary in h ar under reduced pressure yielded the final product, 45

Specific ester COmDOSitiOHS embodied by the which, when isolated, was a water-white, waterinvention, and their method of preparation, are insoluble, viscous liquid, h new ester may be shown in he f l w examplestermed ethylene glycol monoacetate benzoyl lac- Emmple I tate. This ester boiled at 205 to 210 C. at 10 mm. pressure, and had a specific gravity of 1.200 50 met y yco monoacetate in an a ou t at 20/20 C. The identity of the ester was verioi! 2440 grams (16.5 mols) was heated with 1125 fled by its saponification equivalent of 92.2. grams (7.5 mols) oi tartaric acid in the presence The above examples are representative of many 0! sillf fl m as a catalyst. and with benzene other compounds 01' the class embodied in this as the water-removing agent. The maximum reinvention. The process as shown for preparing 55 them, may be modified to suit the particular reactants employed, and the invention should not be limited other than as defined in the appended claims.

We claim:

1. As chemical compounds, esterification products of an aliphatic monocarboxylic acid monoester of a glycol of the group consisting of alkylene and polyalkylene glycols, and an acylated hydroxy acid, wherein the acylating radical corresponds to a monocarboxylic acid.

2. As chemical compounds, esters 0! hydroxy carboxylic acids, in which the hydrogen 01' each carboxyl group is replaced with the radical of an aliphatic monocarboxylic acid monoester of a glycol of the group consisting of alkylene and polyalkylene glycols, and in which the hydrogen of each hydroxyl group is substituted by an acyl radical corresponding to a monocarboxylic acid.

3. As chemical compounds, esters of hydroxy carboxylic acids, in which the hydrogen of each carboxyl group is replaced with the radical of an aliphatic monocarboxylic acid monoester of a glycol of the group consisting of alkylene and polyalkylene glycols, and an aliphatic monocarboxylic acyl radical is substituted for the hydrogen of each hydroxy] group.

4. As chemical compounds, esters of hydroxy carboxylic acids, in which the hydrogen of each carboxyl group is replaced with the monoacetate ester radical of a glycol 01 the group consisting of alkylene and polyalkylene glycols, and an aliphatic monocarboxylic acyl radical is substituted for the hydrogen of each hydroxy] group.

5. As chemical compounds, esters of hydroxy carboxylic acids, in which the hydrogen of each carboxyl group is replaced with the monobutyrate ester radical of a glycol of the group consisting of alkylene and polyalkylene glycols, and an aliphatic monocarboxylic acyl radical is substitued for the hydrogen of each hydroxy] group.

- 6. As chemical compounds, esters of hydroxy carboxylic acids, in which the hydrogen 0! each carboxyl group is replaced with the radical of an v aliphatic carboxylic acid monoester of diethylene glycol, and a monocarboxylic acyl radical is substitut-ed for the hydrogen of each hydroxyl group.

7, As chemical compounds, esters of hydroxy carboxylic acids, in which the hydrogen of each carboxyl group is replaced with the radical of an aliphatic carboxylic acid monoester of propylene glycol, and a monocarboxylic acyl radical is substituted for the hydrogen 0! each hydroxy] group.

8. As a chemical compound, an ester of tartaric acid, in which the hydrogen of both carboxyl groups is replaced with a diethylene glycol monoacetate radical, and an acetyl radical is substituted Iorthe hydrogen of both hydroxyl groups.

9. As a chemical compound, an ester of lactic acid, in which the hydrogen of the carboxyl group is replaced with a propylene glycol monobutyrate radical, and av butyryl radical is substituted for the hydrogen of the hydroxy] group.

10. As a chemical compound, an ester of lactic acid, in which the hydrogen of the carboxyl group is replaced with an ethylene glycol monoacetate radical, and a benzoyl radical is substituted for the hydrogen of the hydroxy] group.

11. As a chemical compound, di-(glycol monoacetate) diacetyl tartrate.

12. Process for making esterification products, which comprises reacting an aliphatic monocarboxylic acid monoester of a glycol of the group consisting of alkylene and polyalkylene glycols with a hydroxy carboxylic acid, and subsequently acylating the reaction product with an acylating agent corresponding to a monocarboxylic acid.

13. Process for making esterification products, which comprises reacting an aliphatic monocarboxylic acid monoester of a glycol of the group consisting of alkylene and polyalkylene glycols with an aliphatic hydroxy carboxylic acid, and subsequently acylating the reaction product with an acylating agent corresponding to a monocarboxylic acid.

14. Process for making esterification products, which comprises reacting an aliphatic monocarboxylic acid monoester of a glycol of the group consisting of alkylene and polyalkylene glycols with -an aliphatic hydroxy carboxylic acid, and

subsequently acylating the reaction product with an aliphatic monocarboxylic acid.

THOMAS F. CARRUTI-IERS. CHARLES M. BLAIR. 

